Efficient Enantioselective Reactions of carbanions α to the Sulfur Functional Groups

碳负离子 α 与硫官能团的高效对映选择性反应

• 批准号: 11650890
• 负责人: TORU Takeshi
• 金额: $ 1.92万
• 依托单位: Nagoya Institute of Technology
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1999
• 资助国家: 日本
• 起止时间: 1999 至 2000
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-11650890/
• 关键词: organosulfur compound; asymmetric synthesis; β-silylethyl sulfoxide; α-sulfinyl carbanion; α-sulfenyl carbanion; enantioseelective reaction; rotational barrier; crysanthemic acid; 有機硫黄化合物; 不斉合成反応; β-シリルエチルスルホキシド; α-スルフィニルカルボアニオン; 菊酸

Since 1999, we have studied on the new asymmetric syntheses using organosulfur sompounds. We stucceeded in developing of new diastereoselective reactions of the α-sulfinyl carbanion derived from β-silylethyl sulfoxides, which afforded only a single diastereoisomer in each reaction using aldehydes, and α, β-unsaturated carbonyl compounds. Furthermore, subsequent reaction of the formed enolates with aldehydes also afforded only a single stereoisomer These results strikingly show that these reactions can control the stereochemistry of the four consecutive chiral centers by a chiral sulfoxide.Enantioselective reactions α-sulfenyl carbanions were also studied. Reactions of α-sulfenyl carbanion with various electrophiles in the presence of chiral bisoxazolines. We examined the reactions with aldehydes, ketones, methyl trifluoromethylsulfonate, trimethylsilyl chloride, and carbon dioxide. The reaction of α-sulfenyl carbanion derived from α-stannylbenzyl phenyl sulfide was found that the react … More ion proceeds through a dynamic kinetic resolution pathway. On the other hand, α-sulfenyl carbanion derived from 2-pyridyl sulfide afforded the product having the stereochemistry opposite to the one obtained in the reaction of benzyl phenyl sulfide. This reaction was proved to proceed through a dynamic thermodynamic resolution pathway with inversion of configuration of the intermediate lithium complex.Furthermore, we have studied on the asymmetric reaction caused by the rotational barrier around the C-S bond axis. The 1-sulfinyl-2-formyl and 2-acylnaphthalenes having the 2,4,6-triisopropylphenyl group showed extremely high stereoselectivities in the nucleophilic reactions, Mukaiyama aldol reactions, and reductions. These stereoselectivities are shown to be caused by the rotational barrier around the C-S bond axis by tire ^1H NMR spectra, the X-ray structural analyses and the MO calculations. Elimination of the sulfinyl group from the obtained products afforded chiral alcohol derivatives. Less

自1999年以来，我们一直致力于有机硫化合物的不对称合成研究。本文研究了由β-硅乙基亚砜衍生的α-亚磺酰基负碳离子与醛和α，β-不饱和羰基化合物的非对映选择性反应。此外，所形成的烯醇化物与醛的后续反应也只得到单一的立体异构体。这些结果显著地表明，这些反应可以通过手性亚砜控制四个连续手性中心的立体化学。手性双恶唑啉存在下α-硫基碳负离子与各种亲电试剂的反应。我们研究了与醛，酮，三氟甲基磺酸甲酯，三甲基硅氯，和二氧化碳的反应。研究了α-锡基苄基苯硫醚衍生的α-硫基碳负离子的反应， ...更多信息 离子通过动态动力学拆分途径进行。另一方面，由2-吡啶硫醚衍生的α-硫基负碳离子得到的产物具有与苄基苯基硫醚反应中得到的产物相反的立体化学。该反应是通过动力学拆分途径进行的，中间体锂络合物的构型发生了反转，并对C-S键轴转动势垒引起的不对称反应进行了研究。具有2，4，6-三异丙基苯基的1-亚磺酰基-2-甲酰基和2-酰基萘在亲核反应、Mukaiyama aldol反应和还原中显示出极高的立体选择性。通过~ 1H NMR谱、X射线结构分析和分子轨道计算，证明了这种立体选择性是由C-S键轴周围的转动势垒引起的。从所得产物中消除亚磺酰基得到手性醇衍生物。少

项目成果

Shuichi Nakamura: "Highly enantioselective reactions of configurationally labile a-thioorganolithiums using chiral bis (oxazoline)s via two different enentiodetermining steps"J.Am.Chem.Soc.. 122. 11340-11347 (2000)

Shuichi Nakamura：“通过两个不同的对映体测定步骤，使用手性双（恶唑啉）对构型不稳定的α-硫代有机锂进行高度对映选择性反应”J.Am.Chem.Soc.. 122. 11340-11347 (2000)

Shuichi Nakamura, Masayuki Kuroyanagi, Yoshihiko Watanabe, and Takeshi Toru: "1,4-Asymmetric Reduction of γ-Ketosulfoxides Bearing the 2,4,6-Triisopropylphenyl Group."J.Chem.Soc., Perkin Trans.. 1, No.18. 3143-3148 (2000)

Shuichi Nakamura、Masayuki Kuroyanagi、Yoshihiko Watanabe 和 Takeshi Toru：“带有 2,4,6-三异丙基苯基的 γ-酮亚砜的 1,4-不对称还原。”J.Chem.Soc.，Perkin Trans.. 1，No .18.3143-3148（2000）

Shuichi Nakamura: "New Asymmetric Reactions of 2-Formyl-and 2-Acyl-1-[(2,4,6-triisopropylphenyl) sulfinyl] naphthalenes via Diastereomeric Rotamers."J.Org.Chem.. 65. 8640-8650 (2000)

Shuichi Nakamura：“通过非对映异构旋转异构体进行 2-甲酰基-和 2-酰基-1-[(2,4,6-三异丙基苯基)亚磺酰基]萘的新不对称反应。”J.Org.Chem.. 65. 8640-8650 (

Shuichi Nakamura, Ryo Nakagawa, Yoshihiko Watanabe, and Takeshi Toru: "Highly Enantioselective Reactions of Configurationally Labile α-Thioorganolithiums Using Chiral Bis (oxazoline)s via Two Different Enantiodetermining Steps."J.Am.Chem.Soc.. 122, No.46.

Shuichi Nakamura、Ryo Nakakawa、Yoshihiko Watanabe 和 Takeshi Toru：“通过两种不同的对映体测定步骤，使用手性双（恶唑啉）对构型不稳定的 α-硫代有机锂进行高度对映选择性反应。”J.Am.Chem.Soc. 122，第 122 期。 46.

Shuichi Nakamura, Ryo Nakagawa, Yoshihiko Watanabe, and Takeshi Toru: "Enantioselective Reactions of Configurationally Unstable α-Thiobenzyllithium Compounds."Angew.Chem.Int.Ed.. 39, No.2. 353-355 (2000)

Shuichi Nakamura、Ryo Nakakawa、Yoshihiko Watanabe 和 Takeshi Toru：“构型不稳定的 α-硫代苄基锂化合物的对映选择性反应”。Angew.Chem.Int.Ed. 39，第 2 期（2000 年）。